A standard NACE hydrogen induced crack test was used to evaluate the resistance of two compositions of X70 steel (X70-X (Ca/S ratio of 2.5) and X70-B (Ca/S ratio of < 0.5)) under severe (pH = 2.7 and 100% H2S) and mild (pH = 5.5 and 100% H2S) sour service conditions. An ultrasonic technique was developed to quantify the severity of hydrogen cracking in both steels as a function of test conditions, steel type and time. In this procedure, a series of local ultrasonic measurements was taken for each test sample to determine a local crack to backwall signal ratio (LCBR). The LCBR values were integrated over the entire sample to give a global crack to backwall ratio (GCBR). A larger GCBR value corresponds to greater hydrogen cracking severity in the sample. Energy dispersive X-ray (EDX) spectroscopy and glancing angle X-ray diffraction (XRD) were used to characterize the surface corrosion products that formed during testing. For severe sour service conditions, the GCBR value reached an asymptotic value of approximately 33% and 47% for X70-X (after 4 days) and X70-B (after 2 days) steels, respectively. For mild sour service conditions, no cracking was observed for testing of less than 16 days. After 32 days, X70-B showed a GCBR of approximately 18%. The onset of cracking of X70-X steel occurred between 32 and 64 days. Samples tested for 64 days showed a GCBR of 30% and 16% for X70-X and X70-B, respectively.
Glancing XRD measurements showed the presence of surface FeS on both steels tested under mild sour service. Quantitative XRD (QXRD) analysis was used to obtain the surface coverage of FeS as a function of test time. EDX mapping confirmed the presence of a high sulfur content over a significant fraction of the surface. XRD measurements of X70-B steel under severe sour service after 8 days did not show a significant amount of FeS. The surface FeS is believed to alter hydrogen ingress into the steel, making it difficult to directly compare measured GCBR values obtained under mild and severe sour service.